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Olefin complexes with electrophiles

The electrophilic activation of a C—C multiple bond as a result of coordination to an electron-deficient metal ion is fundamental to much of organometallic chemistry, both conceptually and in synthetic applications (11). The Wacker process, a classic example of an efficient catalytic oxidation, is an important industrial reaction, used for the conversion of ethylene into acetaldehyde. The catalytic reaction begins with the coordination of ethylene to a Pd(ll) center, leading to activation of the ethylene moiety. The key step is the reaction of the metal-olefin complex with a nucleophile to give substituted metal-alkyl species (12). The integration of this reaction into a productive catalytic cycle requires the eventual cleavage of the newly generated M—C bond. [Pg.5]

Electrophilic attack on olefin ligands coordinated to electron-rich, strongly backbonding metals is illustrated by the reactions of (P group 4 olefin and alkyne complexes, as well as some electron-rich olefin complexes. Zirconocene- and and hafnocene-olefin complexes generated by reaction of zirconocene dichloride with two equivalents of alkyl lithium and isolated upon addition of a phosphine ligand react with carbonyl compounds and weak protic acids to form insertion products and alkyl complexes. Several examples of the reactions of these complexes with electrophiles are shown in Equations 12.65-12.66. Zirconocene-alkyne complexes prepared by thermolysis of vinyl alkyl complexes and titanium-alkyne complexes generated by the reduction of Ti(OPr ) also react with electrophiles, such as aldehydes and acid, to form products from insertion into the M-C bond and protonation of the M-C bond respectively. [Pg.471]

In most palladium-catalyzed oxidations of unsaturated hydrocarbons the reaction begins with a coordination of the double bond to palladium(II). In such palladium(II) olefin complexes (1), which are square planar d8 complexes, the double bond is activated towards further reactions, in particular towards nucleophilic attack. A fairly strong interaction between a vacant orbital on palladium and the filled --orbital on the alkene, together with only a weak interaction between a filled metal d-orbital and the olefin ji -orbital (back donation), leads to an electrophilic activation of the alkene9. [Pg.654]

An important finding is that all peroxo compounds with d° configuration of the TM center exhibit essentially the same epoxidation mechanism [51, 61, 67-72] which is also valid for organic peroxo compounds such as dioxiranes and peracids [73-79], The calculations revealed that direct nucleophilic attack of the olefin at an electrophilic peroxo oxygen center (via a TS of spiro structure) is preferred because of significantly lower activation barriers compared to the multi-step insertion mechanism [51, 61-67]. A recent computational study of epoxidation by Mo peroxo complexes showed that the metallacycle intermediate of the insertion mechanism leads to an aldehyde instead of an epoxide product [62],... [Pg.293]

Density functional calculations reveal that epoxidation of olefins by peroxo complexes with TM d° electronic configuration preferentially proceeds as direct attack of the nucleophilic olefin on an electrophilic peroxo oxygen center via a TS of spiro structure (Sharpless mechanism). For the insertion mechanism much higher activation barriers have been calculated. Moreover, decomposition of the five-membered metallacycle intermediate occurring in the insertion mechanism leads rather to an aldehyde than to an epoxide [63]. [Pg.318]

Several reaction sequences have been reported in which Fischer-type carbene complexes are converted in situ into non-heteroatom-substituted carbene complexes, which then cyclopropanate simple olefins [306,307] (Figure 2.22). This can, for instance, be achieved by treating the carbene complexes with dihydropyridines, forming (isolable) pyridinium ylides. These decompose thermally to yield pyridine and highly electrophilic, non-heteroatom-substituted carbene complexes (Figure 2.22) [46]. [Pg.45]

In cyclopropanations with electrophilic carbene complexes, yields of cyclopropanes tend to improve with increasing electron density of the alkene. As illustrated by the examples in Table 3.5, cyclopropanations of enol ethers with aryldiazomethanes often proceed in high yields. Simple alkyl-substituted olefins are, however, more difficult to cyclopropanate with diazoalkanes. A few examples of the cyclopropanation of enamines with diazoalkanes have been reported [650]. [Pg.115]

Ylides other than acceptor-substituted diazomethanes have only occasionally been used as carbene-complex precursors. lodonium ylides (PhI=CZ Z ) [1017,1050-1056], sulfonium ylides [673], sulfoxonium ylides [1057] and thiophenium ylides [1058,1059] react with electrophilic transition metal complexes to yield intermediates capable of undergoing C-H or N-H insertions and olefin cyclopropanations. [Pg.176]

Fig. 4.18. Possible mechanism of the olefination of thiocarbonyl compounds with electrophilic carhene complexes [1336]. Fig. 4.18. Possible mechanism of the olefination of thiocarbonyl compounds with electrophilic carhene complexes [1336].
The reactivity of peroxo metal complexes as nucleophilic oxidants is a known process ". To visualize this type of reactivity one has to refer to peroxo metal complexes as a 1,3-dipolar reagent M+-0-0 interacting in a bimolecular fashion with electrophilic dipo-larophiles such as electron-poor olefins " (equation 15), to form peroxymetallacycle intermediates. [Pg.1072]

Stmctural features of olefin cycloadducts (i.e., isoxazolines) were extended when regioselective 4-endo- and 3 -exo-deprotonations were discovered, with the broad range of ensuing reactions of these carbanions that are common with electrophiles (19-22, 26-28). Thus, sequences consisting of cycloaddition-modification-ring cleavage were utilized to build up complex structures (17, 20-23). [Pg.363]

Elimination of the positive charge after the electrophilic attack on the olefin by proton removal is observed also in Scheme 28 between ( )-2,2,3,4,5,5-hexamethylhex-3-ene (58) and bromine. The CT complex shown in Scheme 28 probably turns into a second complex (with the ratio 1 2 of 58 and bromine) which ionizes to a bromonium/tribromide ion pair. [Pg.390]

Analogous intramolecular chelation-controlled ketone/olefin couplings with Sml2, in which Sm+3 was complexed in a cyclic manner to the ketyl anion and a /1-carbonyl of an ester or amide functionalilty, were reported as early as 1987 (Scheme 31)86. The cyclized samarium intermediate 49 could be further reacted with added electrophiles such... [Pg.1311]

The ylid character of X5-phosphorins and their Cr(C0)3 complexes again is evident when one or both groups on phosphorus are CHR2 as one can abstract a+ protpn giving a carbanion. Reaction with electrophiles (e.g. D, CH3, and RCHO) causes side chain addition. No Wittig olefination is found with aldehydes. Instead a 1(2 -hydroxy) product 9 is formed which can be dehydrated to the X5-phosphorin derivative 10. [Pg.466]

Such J-mctals as Cu(I) [but not Cu(II)], form a variety of compounds with ethenes, for example [Cu(C2H4)(H20)2]C104 (from Cu, Cu2+, and C2H4) or Cu(C2H4)(bipy)+. It is necessary to mention that, of all the metals involved in biological systems, only copper reacts with ethylene [74b]. Such homoleptic alkene complexes can be useful intermediates for the synthesis of other complexes. The olefin complexes of the metals in high formal oxidation states are electron deficient and therefore inert toward electrophilic reagents. By contrast, the olefin complexes of the metals in low formal oxidation states are attacked by electrophiles such as protons at the electron-rich metal-carbon a-bonds [74c]. [Pg.170]


See other pages where Olefin complexes with electrophiles is mentioned: [Pg.384]    [Pg.384]    [Pg.170]    [Pg.108]    [Pg.363]    [Pg.250]    [Pg.233]    [Pg.183]    [Pg.745]    [Pg.309]    [Pg.407]    [Pg.8]    [Pg.205]    [Pg.238]    [Pg.240]    [Pg.89]    [Pg.106]    [Pg.464]    [Pg.224]    [Pg.324]    [Pg.411]    [Pg.124]    [Pg.515]    [Pg.3]    [Pg.968]    [Pg.183]    [Pg.138]    [Pg.745]    [Pg.659]    [Pg.197]    [Pg.1228]    [Pg.18]    [Pg.197]    [Pg.278]    [Pg.164]   
See also in sourсe #XX -- [ Pg.384 , Pg.385 ]




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Complexes with olefins

Electrophiles olefins

Olefin complexation

Olefin complexes

Olefines, complexes

Reactions of Olefin Complexes with Electrophiles

With Electrophiles

With Olefins

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